CN103367754A - Soft-package aqueous lithium iron phosphate power battery and making method thereof - Google Patents
Soft-package aqueous lithium iron phosphate power battery and making method thereof Download PDFInfo
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- CN103367754A CN103367754A CN2013103225712A CN201310322571A CN103367754A CN 103367754 A CN103367754 A CN 103367754A CN 2013103225712 A CN2013103225712 A CN 2013103225712A CN 201310322571 A CN201310322571 A CN 201310322571A CN 103367754 A CN103367754 A CN 103367754A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a soft-package aqueous lithium iron phosphate power battery. The positive electrode material of the battery comprises the solvent, lithium iron phosphate, the conductive agent and a positive-electrode aqueous binder according to a mass ratio of (70-100):(85-92):(4-7):(3-10); the negative electrode material of the battery comprises a solvent, an active substance, a conductive agent and a negative-electrode aqueous binder according to a mass ratio of (100-130):(90-95):(1-3):(3-7); the active substance is mesocarbon microbeads or graphite or a silicon-carbon alloy or lithium titanate; the conductive agent is a carbon black conductive agent or a graphite conductive agent; the positive-electrode aqueous binder is an aqueous dispersion of an acrylonitrile multipolymer; the negative-electrode aqueous binder is one or a mixture comprising two of styrene butadiene rubber and sodium carboxycellulose; and the battery is a laminated soft package battery. In the invention, an adhesive shortage problem of an oily lithium ion battery is solved, and the battery making cost is effectively reduced on the premise of guaranteeing the performances of the battery.
Description
Technical field
The present invention relates to technical field of lithium ion, be specifically related to a kind of flexible package water system lithium iron phosphate electrokinetic cell and preparation method thereof.
Background technology
Along with the continuous minimizing of traditional non-renewable energy resources, and the continuous appearance of global environment deterioration problem, the mankind also become more and more urgent to research and development of new sources of energy.Lithium ion battery becomes one of study hotspot in recent years with advantages such as its high-energy-density, energy-efficient, environment friendly, in numerous lithium ion battery kinds, ferric phosphate lithium cell has a extensive future at large-sized power battery and energy storage field with its Stability Analysis of Structures, pollution-free, the advantage such as fail safe good, the life-span is long.
It is that glue polyvinylidene fluoride proportioning uses the preparation of 1-METHYLPYRROLIDONE solvent anodal that the interior lithium ion battery of present industry uses oil more, but the existing market polyvinylidene fluoride is short, needs import, on the high side, and the cost of 1-METHYLPYRROLIDONE is high.
Summary of the invention
The technical problem to be solved in the present invention is a kind of flexible package water system lithium iron phosphate electrokinetic cell of exploitation, solves the problem of oily series lithium ion battery adhesive shortage, under the prerequisite that guarantees battery performance, effectively reduces the battery cost of manufacture.
A kind of flexible package water system lithium iron phosphate electrokinetic cell, wherein,
The positive electrode of battery comprises solvent, LiFePO4, conductive agent and anodal aqueous binder, and its mass ratio is (70-100): (85-92): (4-7): (3-10);
The negative material of battery comprises solvent, active material, conductive agent and negative pole aqueous binder, and its mass ratio is (100-130): (90-95): (1-3): (3-7);
Wherein, described solvent is distilled water or deionized water; Described active material is MCMB or graphite or silicon-carbon alloy or lithium titanate; Described conductive agent is the mixture of two kinds of carbon black conductive agent and graphite agent one or both of; Described anodal aqueous binder is the aqueous dispersions of acrylonitrile multiple copolymer; Described negative pole aqueous binder is butadiene-styrene rubber; Described battery is the lamination flexible-packed battery.
Flexible package water system lithium iron phosphate electrokinetic cell of the present invention, the anodal used thickness of wherein said battery is the aluminium foil of 15-25 μ m, the negative pole used thickness is the Copper Foil of 9-16 μ m; Anode ear is aluminium strip or aluminium-to-nickel band, thickness 0.2-0.3mm, width 20-60mm; Negative electrode lug is copper nickel plating, thickness 0.2-0.3mm, width 20-60mm; Aluminum plastic film thickness is 0.113 or 0.152mm.
Flexible package water system lithium iron phosphate electrokinetic cell of the present invention, the barrier film of wherein said battery adopt polyolefin single or multiple lift composite diaphragm, and thickness is 30-40 μ m; Electrolyte is the carbonates multicomponent organic mixture take lithium hexafluoro phosphate as solute.
A kind of method for preparing described flexible package water system lithium iron phosphate electrokinetic cell comprises the steps:
(1) preparation is anodal: use distilled water or deionized water as solvent, LiFePO4, conductive agent and aqueous binder are coated on the aluminium foil after the slurrying in proportion;
(2) preparation negative pole: use distilled water or deionized water as solvent, active material, conductive agent and aqueous binder are coated on the Copper Foil after the slurrying in proportion;
(3) the both positive and negative polarity pole piece is put into the vacuum drying oven baking after punching.
Preparation method of the present invention specifically comprises the steps:
(1) preparation is anodal: at first aqueous binder is dissolved in distilled water or the deionized water, low speed 20Hz stirs 20min; Add LiFePO4 and the conductive agent that is pre-mixed, high speed 50Hz disperses again, and time 4h obtains slurry, and described slurry viscosity is controlled at 4000-6000mPas, is coated on the aluminium foil with automatic coating machine;
(2) preparation negative pole: at first sodium carboxymethylcellulose is dissolved in distilled water or the deionized water, adds butadiene-styrene rubber, low speed 30Hz stirs 30min, add again the negative electrode active material that is pre-mixed, high speed 50Hz disperses, and time 3h is coated on the Copper Foil with automatic coating machine;
(3) the both positive and negative polarity pole piece is put into vacuum drying oven baking 24h after punching, every 4h inflated with nitrogen ventilation, vacuum degree≤0.09Mpa.
Preparation method of the present invention wherein adopts fluid injection behind the battery core baking 48h in the step (3), changes into, partial volume, and electrolyte is LiPF
6Organic solution system, barrier film adopt polyolefin single or multiple lift composite diaphragm, membrane thicknesses 30-40 μ m.
Preparation method of the present invention, baking oven was sectional temperature-controlled when wherein positive plate described in the step (1) was coated with, 30-50 ℃ of 1-3 section temperature, 60-80 ℃ of 4-5 section temperature, 50-70 ℃ of 6-8 section temperature, the coating walking speed is at 3.0-5.0m/min.
Flexible package water system lithium iron phosphate electrokinetic cell difference from prior art of the present invention and beneficial effect:
(1) use aqueous binder to substitute oil binder, present water system glue technology maturation, domestic can be mass, solved the oil binder shortage problem, use distilled water or deionized water to substitute oily series solvent 1-METHYLPYRROLIDONE, reduce cost, more friendly to environment;
Baking oven was sectional temperature-controlled when (2) positive plate was coated with, 30-50 ℃ of 1-3 section temperature, and 60-80 ℃ of 4-5 section temperature, 50-70 ℃ of 6-8 section temperature, oil is low about 20 ℃ of anodal coater oven temperature, energy-saving consumption-reducing reduces the battery cost of manufacture.
(3) adopt the battery of the present invention's preparation, adopt flexible package, played the fail safe of battery high, very light weight improves specific energy, and performance is more excellent.
(4) when reducing the battery cost, using water system technique to prepare the alternative oil of lithium ion battery battery is that technique is more friendly to environment, and it is more green to be applied to electric bus, less to the harm that human health causes.
Below in conjunction with accompanying drawing flexible package water system lithium iron phosphate electrokinetic cell of the present invention is described further.
Description of drawings
Fig. 1 is the battery positive and negative plate design shape figure of the embodiment of the invention 1;
Fig. 2 is the battery design shape figure of the embodiment of the invention 1;
Fig. 3 is the cycle life curve of embodiment 1HPPF10173248/3.2V/30Ah battery;
Fig. 4 is the battery positive and negative plate design shape figure of the embodiment of the invention 2;
Fig. 5 is the battery design shape figure of the embodiment of the invention 2;
Fig. 6 is the cycle life curve of embodiment 2HPPF60100131/3.2V/5Ah battery.
Embodiment
Embodiment 1
Described battery specifications and models are HPPF10173248/3.2V/30Ah.
The below illustrates as an example of the preparation process of HPPF10173248/3.2V/30Ah battery example, battery appearance and pole piece are as illustrated in fig. 1 and 2, the positive electrode of described battery comprises LiFePO4, the super-P(conductive carbon black), the KS-6(electrically conductive graphite), the aqueous dispersions of LA133(acrylonitrile multiple copolymer), deionized water, its mass ratio are 91:4:2:3:80; Negative material comprises MCMB, super-P, and butadiene-styrene rubber, carboxycellulose sodium, the mass ratio of deionized water are 95:2:2:1:130.
The anodal used thickness of described battery is the aluminium foil of 25 μ m, and the negative pole used thickness is the Copper Foil of 16 μ m; Anode ear is aluminium strip or aluminium-to-nickel band, thickness 0.2mm, width 60mm; Negative electrode lug is copper nickel plating, thickness 0.2mm, width 60mm; Aluminum plastic film thickness is 0.152mm.
Battery production method is as follows:
Anodal preparation: LiFePO4, super-P(conductive carbon black), the KS-6(electrically conductive graphite), the aqueous dispersions of LA133(acrylonitrile multiple copolymer) and, the mass ratio of deionized water is 91:4:2:3:80.At first LA133 is dissolved in deionized water, low speed 20Hz stirs 20min; Add LiFePO4 and the conductive agent that is pre-mixed, high speed 50Hz disperses again, and time 4h obtains slurry; Described slurry viscosity is controlled at 4000-6000mPas; Be coated on the aluminium foil with automatic coating machine; Aluminum foil thickness 20 μ m, coated side density 320g/m
2
The negative pole preparation: MCMB, super-P, butadiene-styrene rubber, carboxycellulose sodium, the mass ratio of deionized water are 95:2:2:1:130; At first carboxycellulose sodium is dissolved in deionized water, adds butadiene-styrene rubber, low speed 30Hz stirs 30min; Add the negative electrode active material that is pre-mixed, high speed 50Hz disperses, time 3h again; Be coated on the Copper Foil with automatic coating machine; Copper thickness 12 μ m, coated side density 150g/m
2
The both positive and negative polarity pole piece is put into vacuum drying oven baking 24h after punching, every 4h inflated with nitrogen ventilation, vacuum degree≤0.09MPa; Be assemblied under humidity≤10%RH environment and carry out, adopt laminated structure to make soft-package battery.Fluid injection behind the battery core baking 48h, change into, partial volume, reservoir quantity 180g, electrolyte are LiPF
6Organic solution system, barrier film adopt polypropylene two-layer compound barrier film, membrane thicknesses 40 μ m.
The preparation the high cycle life of battery as shown in Figure 3, its circulation 2400 times, capability retention is still more than 90%.
Embodiment 2
Described battery specifications and models are HPPF60100131/3.2V/5Ah.
The below illustrates as an example of the preparation process of HPPF60100131/3.2V/5Ah battery example, battery appearance and pole piece as shown in Figure 4 and Figure 5, positive electrode comprises LiFePO4, super-P, KS-6, LA133, deionized water, its mass ratio are 86:2:2:10:90; Negative material comprises MCMB, super-P, and butadiene-styrene rubber, carboxycellulose sodium, deionized water, its mass ratio are 91:2:5:2:110.
The anodal used thickness of described battery is the aluminium foil of 15 μ m, and the negative pole used thickness is the Copper Foil of 9 μ m; Anode ear is aluminium strip or aluminium-to-nickel band, thickness 0.3mm, width 20mm; Negative electrode lug is copper nickel plating, thickness 0.3mm, width 20mm; Aluminum plastic film thickness is 0.113mm.
Battery production method is as follows:
Anodal preparation: LiFePO4, super-P, KS-6, LA133, the mass ratio of deionized water are 86:2:2:10:90.At first LA133 is dissolved in deionized water, low speed 20Hz stirs 20min; Add LiFePO4 and the conductive agent that is pre-mixed, high speed 50Hz disperses again, and time 4h obtains slurry; Slurry viscosity is controlled at 4000-6000mPas; Be coated on the aluminium foil with automatic coating machine; Aluminum foil thickness 20 μ m, coated side density 290g/m
2
The negative pole preparation: MCMB, super-P, butadiene-styrene rubber, carboxycellulose sodium, the mass ratio of deionized water are 91:2:5:2:110; At first carboxycellulose sodium is dissolved in deionized water, adds butadiene-styrene rubber, low speed 30Hz stirs 30min; Add the negative electrode active material that is pre-mixed, high speed 50Hz disperses, time 3h again; Be coated on the Copper Foil with automatic coating machine; Copper thickness 12 μ m, coated side density 140g/m
2
The both positive and negative polarity pole piece is put into vacuum drying oven baking 24h after punching, every 4h inflated with nitrogen ventilation, vacuum degree≤0.09MPa; Be assemblied under humidity≤10%RH environment and carry out, adopt laminated structure to make soft-package battery.Fluid injection behind the battery core baking 48h, change into, partial volume, reservoir quantity 30g, electrolyte are lithium hexafluoro phosphate organic solution system, barrier film adopts polypropylene single-layer septum, membrane thicknesses 30 μ m.
The preparation the high cycle life of battery as shown in Figure 6, its circulation 2800 times, capability retention is still more than 90%.
Embodiment 3
In the positive electrode of battery, LiFePO4, super-P(conductive carbon black), the KS-6(electrically conductive graphite) and, the aqueous dispersions of LA133(acrylonitrile multiple copolymer), the mass ratio of deionized water is 85:5:2:8:70;
In the negative material, described active material is graphite, described graphite, and super-P, butadiene-styrene rubber, carboxycellulose sodium, the mass ratio of deionized water are 93:1:4:2:120;
The anodal used thickness of described battery is the aluminium foil of 20 μ m, and the negative pole used thickness is the Copper Foil of 15 μ m; Anode ear is aluminium strip or aluminium-to-nickel band, thickness 0.2mm, width 40mm; Negative electrode lug is copper nickel plating, thickness 0.2mm, width 40mm; Aluminum plastic film thickness is 0.152mm.
Other are with embodiment 1.
We have changed negative material and positive and negative pole material proportioning this example, and implementation result is with embodiment 1.
Embodiment 4
In the positive electrode of battery, LiFePO4, super-P(conductive carbon black), the KS-6(electrically conductive graphite) and, the aqueous dispersions of LA133(acrylonitrile multiple copolymer), the mass ratio of deionized water is 92:3:2:3:100;
In the negative material, described active material is lithium titanate, described lithium titanate, and super-P, butadiene-styrene rubber, carboxycellulose sodium, the mass ratio of deionized water are 90:3:5:2:100;
The anodal used thickness of described battery is the aluminium foil of 18 μ m, and the negative pole used thickness is the Copper Foil of 10 μ m; Anode ear is aluminium strip or aluminium-to-nickel band, thickness 0.3mm, width 30mm; Negative electrode lug is copper nickel plating, thickness 0.3mm, width 30mm; Aluminum plastic film thickness is 0.113mm.
Other are with embodiment 2.
We have changed negative material and positive and negative pole material proportioning this example, and implementation result is with embodiment 2.
Above-described embodiment is described preferred implementation of the present invention; be not that scope of the present invention is limited; design under the prerequisite of spirit not breaking away from the present invention; various distortion and improvement that those of ordinary skills make technical scheme of the present invention all should fall in the definite protection range of claims of the present invention.
Claims (7)
1. flexible package water system lithium iron phosphate electrokinetic cell is characterized in that:
The positive electrode of battery comprises solvent, LiFePO4, conductive agent and anodal aqueous binder, and its mass ratio is (70-100): (85-92): (4-7): (3-10);
The negative material of battery comprises solvent, active material, conductive agent and negative pole aqueous binder, and its mass ratio is (100-130): (90-95): (1-3): (3-7);
Wherein, described solvent is distilled water or deionized water; Described active material is MCMB, graphite, silicon-carbon alloy or lithium titanate; Described conductive agent is the mixture of two kinds of carbon black conductive agent and graphite agent one or both of; Described anodal aqueous binder is the aqueous dispersions of acrylonitrile multiple copolymer; Described negative pole aqueous binder is the mixture of two kinds in butadiene-styrene rubber and carboxycellulose sodium one or both of; Described battery is the lamination flexible-packed battery.
2. flexible package water system lithium iron phosphate electrokinetic cell according to claim 1, it is characterized in that: the anodal used thickness of described battery is the aluminium foil of 15-25 μ m, the negative pole used thickness is the Copper Foil of 9-16 μ m; Anode ear is aluminium strip or aluminium-to-nickel band, thickness 0.2-0.3mm, width 20-60mm; Negative electrode lug is copper nickel plating, thickness 0.2-0.3mm, width 20-60mm; Aluminum plastic film thickness is 0.113 or 0.152mm.
3. flexible package water system lithium iron phosphate electrokinetic cell according to claim 1 and 2 is characterized in that: the barrier film of described battery adopts polyolefin single or multiple lift composite diaphragm, and thickness is 30-40 μ m; Electrolyte is the carbonates multicomponent organic mixture take lithium hexafluoro phosphate as solute.
4. a method for preparing the described flexible package water system lithium iron phosphate of above-mentioned any claim electrokinetic cell is characterized in that: comprise the steps:
(1) preparation is anodal: use distilled water or deionized water as solvent, LiFePO4, conductive agent and aqueous binder are coated on the aluminium foil after the slurrying in proportion;
(2) preparation negative pole: use distilled water or deionized water as solvent, active material, conductive agent and aqueous binder are coated on the Copper Foil after the slurrying in proportion;
(3) the both positive and negative polarity pole piece is put into the vacuum drying oven baking after punching.
5. preparation method according to claim 4 is characterized in that: specifically comprise the steps:
(1) preparation is anodal: at first aqueous binder is dissolved in distilled water or the deionized water, low speed 20Hz stirs 20min; Add LiFePO4 and the conductive agent that is pre-mixed, high speed 50Hz disperses again, and time 4h obtains slurry, and described slurry viscosity is controlled at 4000-6000mPas, is coated on the aluminium foil with automatic coating machine;
(2) preparation negative pole: at first sodium carboxymethylcellulose is dissolved in distilled water or the deionized water, adds butadiene-styrene rubber, low speed 30Hz stirs 30min, add again the negative electrode active material that is pre-mixed, high speed 50Hz disperses, and time 3h is coated on the Copper Foil with automatic coating machine;
(3) the both positive and negative polarity pole piece is put into vacuum drying oven baking 24h after punching, every 4h inflated with nitrogen ventilation, vacuum degree≤0.09Mpa.
6. preparation method according to claim 5, it is characterized in that: adopt fluid injection behind the battery core baking 48h in the step (3), change into, partial volume, electrolyte is LiPF6 organic solution system, and barrier film adopts polyolefin single or multiple lift composite diaphragm, membrane thicknesses 30-40 μ m.
7. according to claim 4 or 5 or 6 described preparation methods, it is characterized in that: baking oven is sectional temperature-controlled during the coating of positive plate described in the step (1), 30-50 ℃ of 1-3 section temperature, 60-80 ℃ of 4-5 section temperature, 50-70 ℃ of 6-8 section temperature, the coating walking speed is at 3.0-5.0m/min.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103700810A (en) * | 2013-12-27 | 2014-04-02 | 安徽亿诺新能源有限责任公司 | Preparation technology of negative electrode of lithium secondary battery |
| CN104795598A (en) * | 2015-05-03 | 2015-07-22 | 鲁奎 | Preparation method of lithium ion battery |
| CN105720267A (en) * | 2016-04-05 | 2016-06-29 | 湖北宇能动力股份有限公司 | Preparation method of lithium ion phosphate power battery cathode plate |
| CN105810907A (en) * | 2016-04-06 | 2016-07-27 | 湖北宇能动力股份有限公司 | Novel high-safety and high-energy negative electrode and preparation method and application thereof |
| CN106450486A (en) * | 2016-12-15 | 2017-02-22 | 衡阳市鑫晟新能源有限公司 | Preparation technique of aluminum-case lithium-ion battery for mobile phone |
| CN108455551A (en) * | 2018-02-01 | 2018-08-28 | 厦门劦能科技有限公司 | A kind of manufacturing method of lithium iron phosphate positive material and lithium secondary battery using the positive electrode |
| CN109921098A (en) * | 2018-11-20 | 2019-06-21 | 万向一二三股份公司 | A kind of preparation method of aqueous super nano ferric phosphate lithium battery |
| CN111261835A (en) * | 2020-03-04 | 2020-06-09 | 广西卓能新能源科技有限公司 | Lithium iron phosphate positive plate and environment-friendly low-temperature-resistant lithium battery comprising same |
| CN111653831A (en) * | 2020-06-22 | 2020-09-11 | 天能帅福得能源股份有限公司 | Preparation method of high-safety, high-temperature and long-life water-based lithium iron phosphate battery |
| CN113346125A (en) * | 2021-05-31 | 2021-09-03 | 廖福宁 | Lithium ion battery |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103700810A (en) * | 2013-12-27 | 2014-04-02 | 安徽亿诺新能源有限责任公司 | Preparation technology of negative electrode of lithium secondary battery |
| CN104795598A (en) * | 2015-05-03 | 2015-07-22 | 鲁奎 | Preparation method of lithium ion battery |
| CN105720267A (en) * | 2016-04-05 | 2016-06-29 | 湖北宇能动力股份有限公司 | Preparation method of lithium ion phosphate power battery cathode plate |
| CN105810907A (en) * | 2016-04-06 | 2016-07-27 | 湖北宇能动力股份有限公司 | Novel high-safety and high-energy negative electrode and preparation method and application thereof |
| CN106450486A (en) * | 2016-12-15 | 2017-02-22 | 衡阳市鑫晟新能源有限公司 | Preparation technique of aluminum-case lithium-ion battery for mobile phone |
| CN108455551A (en) * | 2018-02-01 | 2018-08-28 | 厦门劦能科技有限公司 | A kind of manufacturing method of lithium iron phosphate positive material and lithium secondary battery using the positive electrode |
| CN109921098A (en) * | 2018-11-20 | 2019-06-21 | 万向一二三股份公司 | A kind of preparation method of aqueous super nano ferric phosphate lithium battery |
| CN111261835A (en) * | 2020-03-04 | 2020-06-09 | 广西卓能新能源科技有限公司 | Lithium iron phosphate positive plate and environment-friendly low-temperature-resistant lithium battery comprising same |
| CN111653831A (en) * | 2020-06-22 | 2020-09-11 | 天能帅福得能源股份有限公司 | Preparation method of high-safety, high-temperature and long-life water-based lithium iron phosphate battery |
| CN113346125A (en) * | 2021-05-31 | 2021-09-03 | 廖福宁 | Lithium ion battery |
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Application publication date: 20131023 |